C-hydroxyalkylation of N-adamantylanilines by hexafluoroacetone and methyl trifluoropyruvate

N-(1-Adamantyl)-4-(1-hydroxy-1-trifluoromethyl- 2,2,2- trifluoroethyl)aniline (III) and N-(1-adamantyl)-4-(1-hydroxy-1-methoxycarbony 1-2,2,2-trif luoroethyl) aniline (IV) were obtained by the reaction of N-(1-adamantyl)aniline with ketone (I) and ketoester (II). Analogous procedures gave N-(2-adamantyl)- 4- (1-hydroxy- 1-trifluoromethyl- 2, 2,2-trifluoroethyl)aniline (V) and N-(2-adamantyl)-4-(1-hydroxy-1-methoxycarbonyl-2,2,2-trifluoroethyl)aniline (VI). The action of hydrogen peroxide on (III) in the presence of sodium tungstenate gave N- (1- adamantyl)- 4- (1- hydroxy- 1- trifluoromethyl- 2,2,2- trifluoroethyl)aniline N-oxide (VII).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2348–2350, October, 1989.     

Electronic structure and models of receptor of monooxygenase inductors from a number of polychlorinated polycyclic compounds. IV. MNDO calculations of halogen-substituted azobenzenes

The electron and geometric structures of the cis and trans isomers of 3,3,4,4-tetrachloroazobenzene (3,3,4,4-TCAB) and the trans isomers of 3,3,5,5-TCAB and 3,3-dichloro-4,4-difluoroazobenzene were calculated by the MNDO method. It was established that the trans isomer, which has a planar structure, is most stable for 3,3,4,4-TCAB. Change in the position of the Cl atoms in the azobenzene, i.e., the transition from 3,3,4,4-TCAB to 3,3,5,5-TCAB, does not lead to appreciable change in the formation energy, the position of the electronic levels, the nature of the frontier orbitals, or the charge distribution in the molecules. This gives reason to suggest that the biological activity of 3,3,4,4-TCAB is due to the metabolism products and not to the action of the substrates themselves.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1797–1801, August, 1990.     

Addition of thiols to ethyl 4,4,4-trifluorocrotonate

Ethyl 4,4,4-trifluorocrotonate 1 readily adds aliphatic and aromatic thiols and aminothiols at the double bond in the presence of catalytic amounts of alkylamines and ammonia to give 3-thiolation products. Thiolacetic acid reacts with ester 1 in the absence of a catalyst at 100 °C.     

5-Amino-3,3-bis(trifluomethyl)-1-phenyl-4-cyano-4-pyrazoline

Conclusions The reaction of phenylhydrazine with 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene leads to 5-amino-3,3-bis(trifluoromethyl)-1-phenyl-4-cyano-4-pyrazoline, whose structure was proven by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2417–2419, October, 1988.     

Dynamooptical and electrooptical properties of poly(methylphenylsiloxane) in solution and bulk

The dynamooptical, electrooptical, and hydrodynamic properties of a low-molecular-mass poly(methylphenylsiloxane) containing 33% phenyl radicals (with respect to the total amount of side groups) in dilute solutions and in bulk are studied. The size of macromolecules, as well as the molecular mass of the polymer, its shear optical coefficients Δn/Δτ = (0.29 ± 0.3) × 10^?10 (in decalin) and (0.43 ± 0.03) × 10^?10 cm s²/g (in bulk), and the specific Kerr constants K = (2.30 ± 0.02) × 10^?12 (in benzene), (2.23 ± 0.02) × 10^?12 (in decalin), and (2.24 ± 0.09) × 10^?12 cm⁵/[g (300 V)²] (in bulk), are estimated and compared with the corresponding characteristics of poly(dimethylsiloxane). The effect of solvents on the intramolecular mobility, optical anisotropy, and dipole structure of polymer macromolecules is considered.     

Atmospheric pressure ion focusing with a vortex stream

For successful operation of ionization analysis techniques an efficient sampling and sample ion transportation into an analytical path are required. This is of particular importance for atmospheric pressure ionization sources like corona discharge, electrospray, MALDI, ionization with radioactive isotopes (³H, ⁶³Ni) that produce nonuniform spatial distribution of sample ions. The available methods of sample ion focusing with electric fields are either efficient at reduced pressure (to 1 Torr) or feature high sample losses. In this paper we suggest to use a highly whirled gas stream for atmospheric pressure ion focusing. We use a ⁶³Ni radioactive source to produce an ionized bipolar sample at atmospheric pressure. It is shown by experiments that compared to an aspiration method a forced highly whirled vortex stream allows one to enhance the efficiency of remote ionized sample collection at distances equal to the vortex sampler diameter by an order of magnitude. With a vortex stream, a sixfold increase in the efficiency of the radial ionized sample collection has been obtained. It may be deduced that with the vortex stream remote sampling obtains a new feature which is characterized by a considerable enhancement of the efficiency of the ionized sample collection and can be called as a “gas-dynamic” ionized sample focusing. Considered is the effect of recombination losses of the ionized sample during the remote sampling thereof with the vortex sampler. Prospects for a practical implementation of the vortex sampler for solving the problems of the customs control over the smuggling of radioactive α and β sources are made based on the research results.     

Reactions of α-trifluoromethyl-β-chloroethylsulfenyl chloride with phenols and their derivatives

In the absence of a catalyst, -trifluoromethyl--chloroethylsulfenyl chloride reacts electrophilically with ortho-para-substituted phenols bearing substituents of the first type. The reaction conditions are determined by the C-nucleophilic properties of the phenol, and the selectivity by solvent effects. These -trifluoromethyl--chloroethylthiolated phenols are shown to be highly prone to dehydrochlorination.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 832–837, April, 1990.     

2,5-bis(trifluoromethyl)-1,3,4-oxadiazole in cycloaddition reactions

The cycloaddition of 2,5-bis(trifluoromethyl)-1,3,4-oxadiazole to dienophiles with cyclic and acyclic structures takes place according to a two-step mechanism with the extrusion of nitrogen and results in the formation of derivatives of 7-oxabicyclo [2.2.1]heptanes. A significant influence of the donor properties of the dienophiles, as well as of the spatial factors, on the realization of these processes has been discovered. However, solvation efects do not have a significant effect on the formation of the cycloadducts. The regio- and stereoselectivity of the cyclo-addition reactions has been noted.For a preliminary report, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 95–100, January, 1990.